JP2010170151A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner showing superior smear-preventing properties and good low temperature fixability and providing an image of high quality. <P>SOLUTION: The toner is obtained by granulating in an aqueous medium and contains at least: a first resin which is a polyester resin; a second resin present outside the first resin and having a glass transition temperature (°C) higher than the glass transition temperature (°C) of the first resin; and a crystalline polyester resin. In preferred embodiments, the glass transition temperature of the first resin ranges from 40 to 55°C; the glass transition temperature of the second resin ranges from 56 to 80°C; or the second resin is at least one kind selected from among vinyl resin, polyurethane resin, epoxy resin and polyester resin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an image fixing method and an image fixing apparatus, and an image forming method and an image forming apparatus that are suitably used for electrophotography, electrostatic recording, electrostatic printing, and the like.

  Conventionally, in electrophotographic methods, electrostatic recording methods, electrostatic printing methods, etc., dry toners obtained by melt-kneading and pulverizing a toner binder such as a styrene resin, an acrylic resin, and a polyester resin, and a colorant are used. It is used.

  However, in recent years, there has been a strong demand for higher quality, higher image quality, lower temperature fixability, and the like, and conventional pulverized toners cannot meet these requirements. In other words, the pulverized and classified toner has a limit in the refinement of the toner and the yield of pulverization, and there is a problem that it is not possible to efficiently produce a toner having a small particle size, a sharp particle size distribution, and high image quality. there were.

  Therefore, in recent years, development of CP toner (CHEMICAL PREPARED TONER) has been actively performed. As the CP toner, for example, a polymerization toner produced by a suspension polymerization method, an emulsion polymerization aggregation method, a seed polymerization method, a dispersion polymerization method or the like using a vinyl monomer or the like, a polyester prepolymer, or the like is used. Extension toners produced by an extension reaction (see Patent Document 1) and the like have been proposed. Among these, extension toners are particularly excellent in that polyester resins that are advantageous for improving low-temperature fixability are used. .

  However, the toner is formed using a conventional fixing method (see Patent Documents 2 to 3) in which a toner image is formed using the CP toner or the extension method toner and the toner image is fixed with a relatively low nip surface pressure. Fixing an image on transfer paper or the like is inferior in low-temperature fixability compared to the pulverized toner, and in the image forming apparatus, when the transfer paper is fed, the fixed image is transferred by a conveying roller or a paper feed roller. The fixed image discharged from the image forming apparatus is rubbed to cause image degradation such as dirt, and there is a problem that smearing is deteriorated, for example, the clothes are soiled by rubbing with the user's clothes.

  Accordingly, an image fixing method, an image fixing device that can be suitably used in the image fixing method, an image forming method, and an image forming device, which are excellent in smearing property, good in low-temperature fixability, and capable of obtaining a high-quality image. Is not provided yet.

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention provides an image fixing method, an image fixing apparatus that can be suitably used for the image fixing method, and an image forming method, which have excellent smearing properties, good low-temperature fixability, and provide high-quality images. An object of the present invention is to provide an image forming apparatus.

As a result of intensive studies in view of the above problems, the present inventors have obtained the following knowledge. In other words, the image is fixed on the recording medium by passing the toner image through a nip formed by contacting at least two fixing members. At this time, the toner includes a first resin, A second resin that exists outside the first resin, has a glass transition temperature (° C.) higher than the glass transition temperature (° C.) of the first resin, and is incompatible with the first resin. Is used, and the surface pressure of the nip portion is 55 N / cm ² or more, so that the smear property is excellent, the low-temperature fixability is good, and a high-quality image is obtained. It is knowledge.

The present invention is based on the above findings of the present inventors, and means for solving the above problems are as follows. That is,
<1> By passing an image of toner through a nip portion formed by contacting at least two fixing members, the image is fixed on a recording medium,
The toner is present outside the first resin and the first resin, the glass transition temperature (° C.) thereof is higher than the glass transition temperature (° C.) of the first resin, and the first resin And at least a second resin that is incompatible with the resin of
The first resin is a polyester resin,
The image fixing method is characterized in that a surface pressure of the nip portion is 55 N / cm ² or more.
<2> The image fixing method according to <1>, wherein the toner further contains a crystalline polyester resin.
<3> The image fixing method according to any one of <1> to <2>, wherein the polyester resin contains an unmodified polyester resin and a urea-modified polyester resin.
<4> The image fixing method according to any one of <1> to <3>, wherein the image is fixed to the recording medium by passing the recording medium on which the image of the toner is transferred through a nip portion. .
<5> The image fixing method according to any one of <1> to <4>, wherein the second resin in the toner is a vinyl resin.
<6> A toner solution is prepared by dissolving a toner material containing an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an organic solvent. In the aqueous medium, the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium to form an adhesive substrate in the form of particles. The image fixing method according to any one of <1> to <5>, wherein the image fixing method is obtained by removing the organic solvent.
<7> The image fixing method according to any one of <1> to <6>, wherein the nip portion has a surface pressure of 70 to 500 N / cm ² .
<8> The image fixing method according to any one of <1> to <7>, wherein the fixing member is any one of an endless belt and a roller.
<9> From <1> to <8, wherein an intermediate region located between the introduction side end and the discharge side end of the recording medium in the nip portion is positioned substantially on the same straight line as the introduction side end and the discharge side end. > The image fixing method according to any one of the above.
<10> An image contact side fixing member in which an intermediate region located between the introduction side end and the discharge side end of the recording medium in the nip portion is positioned closer to the image side than the introduction side end and the discharge side end. The image fixing method according to any one of <1> to <8>, wherein the image fixing method is located on the side of the image.
<11> The image fixing method according to any one of <1> to <10>, wherein at least a part of a surface of at least one fixing member is heated by a heating unit.
<12> The image fixing method according to any one of <1> to <11>, wherein the volume average particle diameter / number average particle diameter of the toner is 1.20 or less.
<13> The image fixing method according to any one of <1> to <12>, wherein the toner is a color toner.
<14> including fixing an image on a recording medium by passing an image of toner through a nip formed by contacting at least two fixing members;
The toner is present outside the first resin and the first resin, the glass transition temperature (° C.) thereof is higher than the glass transition temperature (° C.) of the first resin, and the first resin And at least a second resin that is incompatible with the resin of
The first resin is a polyester resin,
The image forming method is characterized in that a surface pressure of the nip portion is 55 N / cm ² or more.
<15> The method according to <14>, further comprising: fixing an image on the recording medium by transferring an image of the toner to the recording medium, and passing the recording medium on which the image has been transferred through a nip portion. An image forming method.
<16> toner image forming means for forming a toner image using the electrostatic latent image formed on the photosensitive member with toner;
A nip portion can be formed in contact with each other, and the nip portion includes at least two fixing members capable of fixing the image to a recording medium by passing the toner image.
The toner is present outside the first resin and the first resin, the glass transition temperature (° C.) thereof is higher than the glass transition temperature (° C.) of the first resin, and the first resin And at least a second resin that is incompatible with the resin of
The first resin is a polyester resin,
In the image forming apparatus, the surface pressure of the nip portion is 55 N / cm ² or more.
<17> The image forming apparatus according to <16>, further including a transfer unit that transfers the toner image formed by the toner image forming unit to a recording medium.
<18> The first resin that is a polyester-based resin, and present on the outside of the first resin, the glass transition temperature (° C.) is higher than the glass transition temperature (° C.) of the first resin, And a toner comprising at least a second resin that is incompatible with the first resin and a crystalline polyester resin.

The image fixing method of the present invention fixes an image on a recording medium by passing an image of toner through a nip portion formed by contacting at least two fixing members,
The toner is present outside the first resin and the first resin, the glass transition temperature (° C.) thereof is higher than the glass transition temperature (° C.) of the first resin, and the first resin And at least a second resin that is incompatible with the resin of
The surface pressure of the nip portion is 55 N / cm ² or more.
In the image fixing method, the toner image passes through a nip portion formed by contacting at least two fixing members. The image is fixed on the recording medium. At this time, in the toner, the second resin existing outside the first resin is crushed when the surface pressure of the nip portion is 55 N / cm ² or more, and the second resin The first resin having a glass transition temperature (° C.) lower than the glass transition temperature (° C.) is eluted. As a result, even under low-temperature fixing conditions, a high-quality image having excellent smearing properties and high image density can be obtained.
In the image fixing method of the present invention, the image may be fixed to the recording medium by passing the recording medium onto which the image of the toner has been transferred, through the nip portion. An embodiment in which one resin is a polyester-based resin, an embodiment in which the second resin in the toner is a vinyl-based resin, and the toner includes an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound In which the adhesive base material is produced in the form of particles by reacting, the volume average particle diameter / number average particle diameter of the toner is 1.20 or less, and the surface pressure of the nip is 70 to 500 N The aspect of / cm ² is preferred.

The image fixing apparatus of the present invention can form a nip portion by abutting each other, and has at least two fixing members capable of fixing the image on a recording medium by passing an image of toner through the nip portion. And
The toner is present outside the first resin and the first resin, the glass transition temperature (° C.) thereof is higher than the glass transition temperature (° C.) of the first resin, and the first resin And at least a second resin that is incompatible with the resin of
The surface pressure of the nip portion is 55 N / cm ² or more.
In the image fixing apparatus, at least two fixing members are in contact with each other to form a nip portion. The image by the toner is passed through the nip portion. Then, the image is fixed on the recording medium. At this time, the surface pressure of the nip portion is 55 N / cm ² or more, the second resin existing outside the first resin in the toner is crushed, and the glass transition temperature of the second resin ( The first resin having a glass transition temperature (° C.) lower than (° C.) is eluted. As a result, even under low-temperature fixing conditions, a high-quality image having excellent smearing properties and high image density can be obtained.

The image forming method of the present invention includes fixing an image on a recording medium by passing an image of toner through a nip portion formed by contacting at least two fixing members,
The toner is present outside the first resin and the first resin, the glass transition temperature (° C.) thereof is higher than the glass transition temperature (° C.) of the first resin, and the first resin And at least a second resin that is incompatible with the resin of
The surface pressure of the nip portion is 55 N / cm ² or more.
In the image forming method, the toner image is passed through a nip portion formed by contacting at least two fixing members. Then, the image is fixed on the recording medium. At this time, in the toner, the second resin existing outside the first resin is crushed when the surface pressure of the nip portion is 55 N / cm ² or more, and the second resin The first resin having a glass transition temperature (° C.) lower than the glass transition temperature (° C.) is eluted. As a result, even under low-temperature fixing conditions, a high-quality image with excellent smear and high image density and high sharpness can be formed.
In the image forming method of the present invention, the image by the toner is transferred to the recording medium, and the recording medium on which the image is transferred is passed through the nip portion, thereby fixing the image to the recording medium. You may let them.

An image forming apparatus of the present invention includes a toner image forming unit that forms a toner image from an electrostatic latent image formed on a photoreceptor using toner;
A nip portion can be formed in contact with each other, and the nip portion includes at least two fixing members capable of fixing the image to a recording medium by passing the toner image.
The toner is present outside the first resin and the first resin, the glass transition temperature (° C.) thereof is higher than the glass transition temperature (° C.) of the first resin, and the first resin And at least a second resin that is incompatible with the resin of
The surface pressure of the nip portion is 55 N / cm ² .
In the image forming apparatus, the toner image forming unit forms the toner image by using the electrostatic latent image formed on the photoreceptor using the toner. At least two of the fixing members are in contact with each other to form a nip portion. The image by the toner is passed through the nip portion. Then, the image is fixed on the recording medium. At this time, the surface pressure of the nip portion is 55 N / cm ² or more, and the second resin existing outside the first resin is crushed, and from the glass transition temperature (° C.) of the second resin. The first resin having a low glass transition temperature (° C.) is eluted. As a result, even under low-temperature fixing conditions, a high-quality image with excellent smear and high image density and high sharpness can be formed.
The image forming apparatus may include a transfer unit that transfers the toner image formed by the toner image forming unit to the recording medium.

  According to the present invention, the conventional problems can be solved, the smearing property is excellent, the low-temperature fixability is good, and a high-quality image can be obtained. The image fixing method and the image fixing method can be suitably used. Image fixing apparatus, image forming method, and image forming apparatus can be provided.

FIG. 1 is a schematic explanatory view showing an example of an image fixing device (belt type image fixing device) of the present invention. FIG. 2 is a schematic explanatory view showing an example of the image fixing apparatus of the present invention. FIG. 3 is a schematic explanatory view showing an example of the image fixing device (electromagnetic induction heating type image fixing device) of the present invention. FIG. 4 is a schematic explanatory view showing an example of the image fixing device (transfer simultaneous fixing type image fixing device) of the present invention. FIG. 5 is a schematic explanatory view showing an example of the image fixing device (electromagnetic induction heating type image fixing device) of the present invention. FIG. 6 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 7 is a schematic explanatory view showing another example in which the image forming method of the present invention is implemented by the image forming apparatus of the present invention. FIG. 8 is a schematic explanatory view showing an example of carrying out the image forming method of the present invention by the image forming apparatus (tandem color image forming apparatus) of the present invention. FIG. 9 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG. FIG. 10 is an SEM photograph of the toner base particles obtained in Production Example 1.

(Image fixing method and image fixing apparatus)
The image fixing method of the present invention includes at least a fixing step of fixing an image on a recording medium by passing an image formed of toner through a nip formed by contacting at least two fixing members. Other processes appropriately selected according to the process are included.
The image fixing apparatus according to the present invention has at least two fixing members capable of forming a nip portion in contact with each other and capable of fixing the image onto a recording medium by passing an image of toner through the nip portion. Furthermore, it has other members appropriately selected as necessary.
The toner is present on the outer side of the first resin and the first resin, the glass transition temperature (° C.) is higher than the glass transition temperature (° C.) of the first resin, and the toner Containing at least a second resin that is incompatible with the first resin,
The surface pressure of the nip portion is 55 / cm ² or more.
The image fixing method of the present invention can be preferably carried out using the image fixing apparatus of the present invention. When the image fixing apparatus of the present invention is implemented, the image fixing method of the present invention is implemented.

<Fixing process>
The fixing step is a step of fixing the image on the recording medium by passing an image of toner through a nip portion formed by contacting at least two fixing members.
In the fixing step, the image by the toner may be transferred to the recording medium, and the recording medium on which the image has been transferred may be passed through the nip portion to fix the image to the recording medium. The image may be simultaneously transferred and fixed to the recording medium at the nip portion (transfer simultaneous fixing).
Further, the fixing step may be performed each time the toner of each color is transferred to the recording medium, or may be performed at the same time in a state where the toner of each color is laminated.

-Nip part-
The nip portion is formed by bringing at least two fixing members into contact with each other.
There is no restriction | limiting in particular as the surface pressure of the said nip part, Although it can select suitably according to the objective, It needs to be 55 N / cm < ² > or more, and 70-500 N / cm < ² > is preferable. When the surface pressure of the nip portion is high, the glossiness of the image is improved and color reproducibility is improved by suppressing irregular reflection. On the other hand, if the surface pressure at the nip is less than 55 N / cm ² , the low-temperature fixability and smear properties are inferior, and a high-quality image may not be obtained.

  An intermediate region located between the introduction side end and the discharge side end of the recording medium in the nip portion may be positioned substantially on the same straight line as the introduction side end and the discharge side end. You may be located in the image contact side fixing member side located in a contact side. When the intermediate region is located on the image contact side fixing member side, the discharge of the recording medium from the nip portion is in a direction to separate the image surface from the fixing member, so that the fixing of the recording medium is performed. Winding around the member can be prevented.

-Fixing member-
The fixing member is not particularly limited as long as it can abut against each other to form a nip portion, and can be appropriately selected according to the purpose. For example, a combination of an endless belt and a roller, a roller and a roller, The heating method from the surface of the fixing member by a combination of an endless belt and a roller or induction heating can be used in order to reduce the warm-up time and realize energy saving. It is preferable to use it.
Examples of the fixing member include known heating and pressing means (combination of heating means and pressing means). In the case of a combination of the endless belt and the roller, for example, a combination of a heating roller, a pressure roller, and an endless belt may be used as the heating and pressing unit, and the combination of the roller and the roller may be used. In this case, for example, a combination of a heating roller and a pressure roller can be used.

  When the fixing member is an endless belt, the endless belt is preferably formed of a material having a small heat capacity. For example, an embodiment in which an offset prevention layer is provided on a substrate may be used. Examples of the material for forming the base include nickel and polyimide, and examples of the material for forming the offset prevention layer include silicone rubber and fluorine-based resin.

  When the fixing member is a roller, the cored bar of the roller is preferably formed of an inelastic member to prevent deformation (deflection) due to high pressure. There is no restriction | limiting in particular as this inelastic member, Although it can select suitably according to the objective, For example, high thermal conductivity bodies, such as aluminum, iron, stainless steel, brass, are mentioned suitably. Moreover, it is preferable that the surface of the roller is covered with an offset prevention layer. The material for forming the offset prevention layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include RTV, silicone rubber, tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA), and polytetrafluoro. Preferred examples include ethylene (PTFE).

  The fixing member itself has a heating unit and may function as a heating member, but at least a part of the surface of at least one of the fixing members is heated by the heating unit. preferable. There is no restriction | limiting in particular as such a heating means, According to the objective, it can select suitably, For example, an electromagnetic induction heating means etc. are mentioned.

The electromagnetic induction heating means is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferable to comprise a shielding layer provided with a coil and an insulating layer provided on the opposite side of the surface of the shielding layer on which the induction coil is provided. In this case, it is preferable that the heating roller is formed of a magnetic material or a heat pipe.
The induction coil is arranged in a state of wrapping at least a semi-cylindrical portion on the opposite side of the contact portion between the heating roller and the fixing member (for example, a pressure roller, an endless belt, etc.) of the heating roller. Is preferred.

  The temperature at which the image is fixed to the recording medium by the toner, that is, the surface temperature of the fixing member by the heating unit is not particularly limited and may be appropriately selected depending on the intended purpose. 170 degreeC is preferable and 120-160 degreeC is more preferable. If the fixing temperature is less than 120 ° C, the fixability may be insufficient, and if it exceeds 170 ° C, it is not preferable in terms of realizing energy saving.

-Toner-
The toner is present outside the first resin and the first resin, and has a glass transition temperature (° C.) higher than the glass transition temperature (° C.) of the first resin. And at least a second resin that is incompatible with the resin. In the toner, since the first resin is coated with the second resin that is higher than the glass transition temperature (° C.) of the first resin, the solidification of the toner during storage is prevented, The heat-resistant storage stability is excellent, and the first resin having a low glass transition temperature (° C.) is eluted from the inside of the toner at the time of fixing to a recording medium, which will be described later.
The toner includes at least the first resin and the second resin, preferably includes a crystalline polyester resin, and, if necessary, other components such as a colorant, a release agent, and a charge control agent. including.

  Examples of the toner include toners produced by a known suspension polymerization method, emulsion aggregation method, emulsion dispersion method, dissolution suspension method, and the like. The active hydrogen group-containing compound and the active hydrogen group-containing toner are included. A toner solution containing a polymer capable of reacting with a compound is dissolved in an organic solvent to prepare a toner solution, and then the toner solution is dispersed in an aqueous medium to prepare a dispersion. In the aqueous medium, A toner obtained by reacting the active hydrogen group-containing compound with a polymer capable of reacting with the active hydrogen group-containing compound to form an adhesive substrate in the form of particles and removing the organic solvent is preferable.

[First resin]
As said 1st resin, it does not melt | dissolve with said 2nd resin, but exists inside said 2nd resin, The glass transition temperature (degreeC) is the glass transition temperature of said 2nd resin ( As long as the temperature is lower than (° C.), there is no particular limitation, and it can be appropriately selected according to the purpose. Examples thereof include an adhesive substrate.

-Adhesive substrate-
The adhesive substrate exhibits adhesiveness to a recording medium such as paper, and is formed by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium. It may contain at least a polymer and may further contain a binder resin appropriately selected from known binder resins.

There is no restriction | limiting in particular as a weight average molecular weight of the said adhesive base material, Although it can select suitably according to the objective, For example, 3,000 or more are preferable and 5,000-1,000,000 are more preferable. 7,000 to 500,000 are particularly preferred.
When the weight average molecular weight is less than 3,000, the hot offset resistance may be deteriorated.

There is no restriction | limiting in particular as a glass transition temperature (Tg) of the said adhesive base material, Although it can select suitably according to the objective, For example, 40-55 degreeC is preferable and 45-50 degreeC is more preferable. In the toner, since a polyester resin subjected to a crosslinking reaction and an extension reaction coexists, the toner exhibits good storage stability even when the glass transition temperature is lower than that of a conventional polyester toner.
When the glass transition temperature (Tg) is less than 40 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 55 ° C., the low-temperature fixability may not be sufficient.

  The glass transition temperature can be measured by, for example, the following method using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, about 10 mg of toner is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample is left at 150 ° C. for 10 minutes, and the sample is cooled to room temperature and left for 10 minutes. Then, the DSC curve is measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, using the analysis system in the TG-DSC system TAS-100 system, the glass transition temperature (Tg) is calculated from the contact point between the tangent line of the endothermic curve near the glass transition temperature (Tg) and the baseline. can do.

Specific examples of the adhesive substrate are not particularly limited and may be appropriately selected depending on the intended purpose. Particularly preferred examples include polyester resins.
There is no restriction | limiting in particular as said polyester-type resin, Although it can select suitably according to the objective, For example, a urea modified polyester-type resin etc. are mentioned especially suitably.
The urea-modified polyester-based resin includes an amine (B) as the active hydrogen group-containing compound and an isocyanate group-containing polyester prepolymer (A) as a polymer that can react with the active hydrogen group-containing compound. It is obtained by reacting in a medium.
The urea-modified polyester resin may contain a urethane bond in addition to the urea bond, and in this case, the molar ratio of the urea bond to the urethane bond (urea bond / urethane bond) is particularly limited. However, 100/0 to 10/90 is preferable, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable.
When the urea bond is less than 10, the hot offset resistance may be deteriorated.

  Preferable specific examples of the urea-modified polyester resin include the following (1) to (10), that is, (1) a polyester pre-reacted polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate. A mixture of a polymer urealated with isophorone diamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, and (2) a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer reacted with diisocyanate and uread with isophoronediamine, a bicondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (3) bisphenol A ethylene oxide 2 mol A polyester prepolymer obtained by reacting an adduct / bisphenol A propylene oxide 2 mol adduct and a polycondensate of terephthalic acid with isophorone diisocyanate, and urethanized with isophorone diamine, and bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene. Mixture of oxide 2 mol adduct and polycondensate of terephthalic acid, (4) Bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate were reacted with isophorone diisocyanate. A mixture of a polyester prepolymer uread with isophoronediamine, a bisphenol A propylene oxide 2-mole adduct and a polycondensate of terephthalic acid, (5) bisphenol A A polyester prepolymer obtained by reacting a polycondensate of tylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid (6) Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide with 2 mol of bisphenol A and isophorone diisocyanate with urea and hexamethylenediamine and 2 mol of bisphenol A ethylene oxide. Product / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate, (7) bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate A mixture of a polyester prepolymer reacted with socyanate with urethanized with ethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (8) bisphenol A ethylene oxide 2 mol adduct and isophthalic acid (9) Bisphenol A ethylene, a mixture of a polyester prepolymer obtained by reacting a polycondensate of bisphenol with diphenylmethane diisocyanate and uread with hexamethylene diamine, a bicondensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, Polyester prepolymer obtained by reacting polycondensate of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate Mixture of uremer with hexamethylenediamine and bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate, (10) bisphenol A ethylene oxide 2-mole addition And a mixture of a polyester prepolymer obtained by reacting a polycondensate of isophthalic acid and toluene diisocyanate with urea diisocyanate with hexamethylenediamine, a bicondensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, etc. Preferably mentioned.

-Active hydrogen group-containing compound-
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polymer capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in the aqueous medium.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the purpose. For example, the polymer capable of reacting with the active hydrogen group-containing compound is In the case of the isocyanate group-containing polyester prepolymer (A), the amines (B) can be increased in molecular weight by a reaction such as an elongation reaction or a crosslinking reaction with the isocyanate group-containing polyester prepolymer (A). Is preferred.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, an alcoholic hydroxyl group is particularly preferable.

The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are particularly preferable.

Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the block (B6) in which the amino group of B1 to B5 is blocked include, for example, a ketimine obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) Compounds, oxazolyzone compounds, and the like.

  In addition, a reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, etc. between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound. Use of the reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.) or those blocked (ketimine compounds).

As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amines (B) The mixing equivalent ratio ([NCO] / [NHx]) of the amino group [NHx] is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, It is particularly preferably 1.5 to 1.5 / 1.
When the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may be deteriorated. The hot offset resistance may be deteriorated.

--Polymer capable of reacting with active hydrogen group-containing compound--
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “prepolymer”) is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. However, it can be appropriately selected from known resins, and examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, and derivative resins thereof.
These may be used individually by 1 type and may use 2 or more types together. Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting.

The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, An acid chloride group, and the like.
These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable.

Among the prepolymers, it is easy to adjust the molecular weight of the polymer component, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a heating medium for fixing. It is particularly preferable that it is a urea bond-forming group-containing polyester resin (RMPE) in that it can be secured.
As said urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond-forming group in the urea bond-forming group-containing polyester resin (RMPE) is the isocyanate group, the isocyanate group-containing polyester prepolymer (A) and the like are particularly preferable as the polyester resin (RMPE). It is done.

  The isocyanate group-containing polyester prepolymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), And what made the said active hydrogen group containing polyester resin react with polyisocyanate (PIC), etc. are mentioned.

  There is no restriction | limiting in particular as said polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol A mixture with (TO), etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, the diol (DIO) alone or a mixture of the diol (DIO) and a small amount of the trivalent or higher polyol (TO) is preferable.

Examples of the diol (DIO) include alkylene glycols, alkylene ether glycols, alicyclic diols, alkylene oxide adducts of alicyclic diols, bisphenols, alkylene oxide adducts of bisphenols, and the like.
The alkylene glycol is preferably one having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Can be mentioned. Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adduct of the alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol. Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of the bisphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the bisphenol.
Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols and the like are preferable, and alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Mixtures are particularly preferred.

The trivalent or higher polyol (TO) is preferably 3 to 8 or higher, for example, a trivalent or higher polyhydric aliphatic alcohol, a trivalent or higher polyphenol, a trivalent or higher polyphenol. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, and the like. Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like. Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide to the trihydric or higher polyphenols.

  The mixture mass ratio (DIO: TO) of the diol (DIO) and the trivalent or higher polyol (TO) in the mixture of the diol (DIO) and the trivalent or higher polyol (TO) is 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

There is no restriction | limiting in particular as said polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) ) And a tricarboxylic or higher polycarboxylic acid.
These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of DIC and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.
Examples of the dicarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like.
Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, and sebacic acid. As said alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. As said aromatic dicarboxylic acid, a C8-C20 thing is preferable, For example, a phthalic acid, an isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.

The trivalent or higher polycarboxylic acid (TO) is preferably a trivalent to octavalent or higher one, and examples thereof include aromatic polycarboxylic acids.
The aromatic polycarboxylic acid preferably has 9 to 20 carbon atoms, and examples thereof include trimellitic acid and pyromellitic acid.

  As the polycarboxylic acid (PC), the dicarboxylic acid (DIC), the trivalent or higher polycarboxylic acid (TC), and a mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid, Any acid anhydride or lower alkyl ester selected from can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

  Mixing mass ratio (DIC: TC) of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) in the mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

  The mixing ratio for the polycondensation reaction between the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the polyol (PO) The equivalent ratio ([OH] / [COOH]) of the hydroxyl group [OH] to the carboxyl group [COOH] in the polycarboxylic acid (PC) is usually preferably 2/1 to 1/1. More preferably, it is 0.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyol (PO), Although it can select suitably according to the objective, For example, 0.5-40 mass% is preferable. 1-30 mass% is more preferable, and 2-20 mass% is especially preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by mass. In some cases, the low-temperature fixability may deteriorate.

The polyisocyanate (PIC) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic diisocyanates, araliphatic diisocyanates, and isocyanurates. And those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate and diphenyl ether-4,4′-diisocyanate. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate, triisocyanatocycloalkyl-isocyanurate, and the like.
These can be used alone or in combination of two or more.

As a mixing ratio when reacting the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin), the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and preferably 4/1 to 1.2 / 1. More preferred is 3/1 to 1.5 / 1.
When the isocyanate group [NCO] exceeds 5, low-temperature fixability may be deteriorated, and when it is less than 1, offset resistance may be deteriorated.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5-40 mass% is Preferably, 1-30 mass% is more preferable, and 2-20 mass% is still more preferable.
When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, Low temperature fixability may deteriorate.

The average number of isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A) is preferably 1 or more, more preferably 1.2 to 5, and more preferably 1.5 to 4.
When the average number of the isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

  The weight average molecular weight (Mw) of the polymer capable of reacting with the active hydrogen group-containing compound is 1,000 to 30,000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). Preferably, 1,500-15,000 are more preferable. When the weight average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated, and when it exceeds 30,000, the low temperature fixability may be deteriorated.

The measurement of the molecular weight distribution by the gel permeation chromatography (GPC) can be performed, for example, as follows.
That is, first, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran (THF) as a column solvent is allowed to flow at a flow rate of 1 ml per minute, and 50 to 200 μl of a tetrahydrofuran sample solution of a resin whose sample concentration is adjusted to 0.05 to 0.6 mass% is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve created by several monodisperse polystyrene standard samples and the count number. Examples of standard polystyrene samples for preparing the calibration curve include Pressure Chemical Co. Or the molecular weights made by Toyo Soda Kogyo Co., Ltd. are 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 It is preferable to use those of × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ and use at least about 10 standard polystyrene samples. As the detector, an RI (refractive index) detector can be used.

--- Aqueous medium--
The aqueous medium is not particularly limited and may be appropriately selected from known ones. Examples thereof include water, solvents miscible with water, and mixtures thereof. Among these, Is particularly preferred.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the lower ketones include acetone and methyl ethyl ketone.
These may be used individually by 1 type and may use 2 or more types together.

--Binder resin--
There is no restriction | limiting in particular as said binder resin, According to the objective, it can select suitably, For example, although a polyester resin etc. are mentioned, Undenatured polyester resin (unmodified polyester resin) is especially preferable.
When the unmodified polyester resin is contained in the toner, low-temperature fixability and glossiness can be improved.
Examples of the unmodified polyester resin include those similar to the urea bond-forming group-containing polyester resin, that is, a polycondensate of a polyol (PO) and a polycarboxylic acid (PC). The unmodified polyester resin is partially compatible with the urea bond-forming group-containing polyester resin (RMPE), that is, has a similar structure that is compatible with each other. It is preferable in terms of resistance to hot offset.

The weight average molecular weight (Mw) of the unmodified polyester resin is preferably 1,000 to 30,000, preferably 1,500 to 15, in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). 1,000 is more preferable. When the weight average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated. Therefore, as described above, the content of the component having the weight average molecular weight (Mw) of less than 1,000. Is required to be 8 to 28% by mass. On the other hand, when the weight average molecular weight (Mw) exceeds 30,000, the low-temperature fixability may be deteriorated.
The glass transition temperature of the unmodified polyester resin is usually 30 to 70 ° C, more preferably 35 to 60 ° C, and still more preferably 35 to 50 ° C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may be deteriorated, and when it exceeds 70 ° C., the low-temperature fixability may be insufficient.
The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g, more preferably 10 to 120 mgKOH / g, and still more preferably 20 to 80 mgKOH / g. If the hydroxyl value is less than 5, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is preferably 1.0 to 50.0 mgKOH / g, and more preferably 1.0 to 30.0. Generally, it becomes easy to be negatively charged by giving the toner an acid value.
When the unmodified polyester resin is contained in the toner, the mixing mass ratio (RMPE / PE) of the urea bond-forming group-containing polyester resin (RMPE) and the unmodified polyester resin (PE) is 5/95. -25/75 is preferable, and 10 / 90-25 / 75 is more preferable.
If the mixing mass ratio of the unmodified polyester resin (PE) exceeds 95, the hot offset resistance may be deteriorated, and if it is less than 75, the low-temperature fixability and the glossiness of the image may be deteriorated. .

[Second resin]
As said 2nd resin, as long as it exists outside said 1st resin, and its glass transition temperature (degreeC) is higher than said 1st resin, without being compatible with said 1st resin. There is no restriction | limiting, According to the objective, it can select suitably, For example, resin fine particles etc. are mentioned.

  There is no restriction | limiting in particular as a glass transition temperature (degreeC) of the said resin fine particle, Although it can select suitably according to the objective, For example, 56-80 degreeC is preferable and 60-75 degreeC is more preferable. When the glass transition temperature (° C.) is less than 56 ° C., heat-resistant storage stability may be deteriorated, and when it exceeds 80 ° C., low-temperature fixability may be deteriorated.

The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate. Examples of the resin include vinyl resins. Among these, vinyl resins are particularly preferable.
These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferably formed of at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin in that an aqueous dispersion of fine spherical resin resin particles can be easily obtained.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.
Moreover, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used.
The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). "; Manufactured by Sanyo Chemical Industries Ltd.), divinylbenzene, 1,6-hexanediol acrylate and the like.

  The resin fine particles can be obtained by polymerization according to a known method appropriately selected according to the purpose, but is preferably obtained as an aqueous dispersion of the resin fine particles. The method for preparing the aqueous dispersion of the resin fine particles is, for example, (1) In the case of the vinyl resin, a vinyl monomer is used as a starting material and is selected from suspension polymerization, emulsion polymerization, seed polymerization, and dispersion polymerization. (2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer). Or the like, or a solvent solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant, and then heated or added with a curing agent to be cured to produce an aqueous dispersion of resin fine particles (3) ) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it may be a precursor (monomer, oligomer, etc.) or a solvent solution thereof (liquid). (4) Preliminary polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition) After the resin prepared by any polymerization reaction mode such as condensation and condensation polymerization is pulverized using a mechanical pulverizer or jet type pulverizer and then classified to obtain resin fine particles , A method of dispersing in water in the presence of an appropriate dispersant, (5) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) (6) A polymerization reaction (addition polymerization) in advance, in which resin fine particles are obtained by spraying a resin solution in which the resin is dissolved in a solvent to obtain resin fine particles and then dispersing the resin fine particles in water in the presence of an appropriate dispersant. , Ring-opening polymerization, polyaddition, addition condensation The resin fine particles can be obtained by adding a poor solvent to a resin solution obtained by dissolving a resin prepared in a solvent by a polymerization reaction method such as condensation polymerization or by cooling a resin solution previously dissolved in a solvent by heating. And then removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a suitable dispersant. (7) Polymerization reaction (addition polymerization, ring-opening polymerization, heavy polymerization) in advance (Any polymerization reaction mode such as addition, addition condensation, and condensation polymerization may be used.) A resin solution prepared by dissolving a resin prepared in a solvent in a solvent is dispersed in an aqueous medium and then heated or heated. (8) A resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation or condensation polymerization) is used as a solvent. In the dissolved resin solution A method of dissolving a suitable emulsifier and then adding water to carry out phase inversion emulsification is preferable.

(Crystalline polyester resin)
The crystalline polyester resin has crystallinity and exhibits a heat-melting characteristic that causes a sudden decrease in viscosity near the fixing start temperature. In other words, until the melting start temperature, the heat resistant storage stability is good due to crystallinity, and at the melting starting temperature, a sharp viscosity drop (sharp melt property) occurs and fixing is performed. A compatible toner can be produced. In addition, the mold release width (the difference between the low temperature fixing lower limit temperature and the hot offset occurrence temperature) is also excellent.

  The crystalline polyester is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diol compounds having 2 to 6 carbon atoms as alcohol components, particularly 1,4-butanediol and 1,6. Synthesis using hexanediol and those containing 80 mol% or more, preferably 85 to 100 mol%, and at least maleic acid, fumaric acid, succinic acid and derivatives thereof as acidic components Preferred examples thereof include crystalline polyester resins represented by the following general formula (1).

In the general formula (1), n and m represent the number of repeating units, L represents an integer of 1 to 3, and R ¹ and R ² may be the same as or different from each other. Often represents a hydrogen atom or a hydrocarbon group.

In order to control the crystallinity and softening point of the crystalline polyester resin, when the crystalline polyester is synthesized, a trihydric or higher polyhydric alcohol such as glycerin is used as the alcohol component, trimellitic anhydride is used as the acid component, etc. Non-linear polyesters obtained by condensation polymerization by adding a trivalent or higher polyvalent carboxylic acid may be used. The molecular structure of the crystalline polyester can be confirmed by solid NMR.
The weight average molecular weight (Mw) of the crystalline polyester resin is preferably 1,000 to 30,000, more preferably 1,000 to 6,500 in terms of molecular weight distribution by GPC of the soluble portion of orthodichlorobenzene. When the weight average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated, and when it exceeds 30,000, the low temperature fixability may be deteriorated.
The number average molecular weight (Mn) of the crystalline polyester resin is preferably 500 to 6,000, more preferably 500 to 2,000 in terms of molecular weight distribution by GPC of the soluble part of orthodichlorobenzene. Moreover, as (Mw / Mn), 2-8 are preferable and 2-5 are more preferable.
In the molecular weight distribution by GPC, the peak position of the molecular weight distribution diagram in which the horizontal axis represents log (M) and the vertical axis represents mass% is in the range of 3.5 to 4.0, and the peak half-value width is 1 .5 or less is preferable.

The melting temperature and F1 _{/ 2} temperature of the crystalline polyester resin are preferably low as long as the heat resistant storage stability is not deteriorated. For example, the DSC endothermic peak temperature is preferably 50 to 150 ° C. When the melting temperature and the F _1/2 temperature are less than 50 ° C., the heat-resistant storage stability is deteriorated, and blocking tends to occur at the temperature inside the developing device. Therefore, the low temperature fixability may be deteriorated.

The crystalline polyester resin preferably has an absorption based on at least the olefin to any of the infrared absorption spectrum at 965 ± 10 cm ^-1 and 990 ± 10cm ^-1 δCH (out-of-plane bending vibration). When absorption based on δCH of the olefin is present at the position, the low-temperature fixability is improved.

The acid value of the crystalline polyester is preferably 8 mgKOH / g or more, and more preferably 20 mgKOH / g or more in order to achieve low temperature fixability from the viewpoint of the affinity between paper and resin. On the other hand, in order to improve hot offset property, 45 mgKOH / g or less is preferable.
The hydroxyl value of the crystalline polyester resin is preferably from 0 to 50 mgKOH / g, more preferably from 5 to 50 mgKOH / g, from the viewpoint of improving low-temperature fixability and charging characteristics.

  When the non-modified polyester resin (b) and the crystalline polyester resin (c) are contained in the toner, the urea bond-forming group-containing polyester resin (a), the unmodified polyester resin (b), and the crystalline The mixing mass ratio with the polyester resin (c) is usually (a) / (b) + (c) of 5/95 to 25/75, preferably 10/90 to 25/75, and 12/88 to 25/75 is more preferable, 12/88 to 22/78 is still more preferable, and the mass ratio of (b) to (c) is 99/1 to 50/50, and 95/5 to 60/40. Is preferable, and 90/10 to 65/35 is more preferable. When the mass ratio is out of the numerical range, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat resistant storage stability and low temperature fixability.

[Other ingredients]
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, colorants, mold release agents, charge control agents, inorganic fine particles, fluidity improvers, cleaning improvers, magnetic properties, and the like. Materials, metal soaps, and the like.

The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon.
These may be used individually by 1 type and may use 2 or more types together.

The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass.
When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed, and when the content exceeds 15% by mass, a poor dispersion of the pigment in the toner occurs. The characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic ring Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.
Examples of the waxes include carbonyl group-containing waxes, polyolefin waxes, and long-chain hydrocarbons. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable.
Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.
Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is especially preferable.
If the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability, and if it exceeds 160 ° C., a cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax.
If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 0-40 mass% is preferable and 3-30 mass% is more preferable.
When the content exceeds 40% by mass, the fluidity of the toner may be deteriorated.

The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material may be used. Preferably, for example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxyamines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten Examples thereof include a single substance or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative. These may be used individually by 1 type and may use 2 or more types together.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, phenolic condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), fourth Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR which is a boron complex -147 (manufactured by Nippon Carlit), quinacridone, azo pigments, other sulfonic acid groups, carbo Sill group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.
The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added together with the toner components when directly dissolving or dispersing in the organic solvent, or The toner particles may be fixed on the toner surface after production.

  The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence / absence of an additive, a dispersion method, and the like, and cannot be generally specified. On the other hand, 0.1-10 mass parts is preferable, and 0.2-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large, and the effect of the main charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Examples include silicon and silicon nitride. These may be used individually by 1 type and may use 2 or more types together.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 10 nm to 500 nm. The specific surface area of the inorganic fine particles by BET method is preferably 20 to 500 m ² / g.
The content of the inorganic fine particles in the toner is preferably 0.01 to 5.0% by mass, and more preferably 0.1 to 3.0% by mass.

The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include a silane coupling agent having a fluoroalkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil.
The cleaning improver is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium. For example, a fatty acid metal salt such as zinc stearate, calcium stearate, stearic acid, Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as methyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

As an example of the method for producing the toner, a method for obtaining the toner by forming the adhesive base material in the form of particles will be described below.
In the method of granulating the toner by forming the adhesive substrate into particles, for example, preparation of an aqueous medium phase, preparation of a toner solution, preparation of a dispersion, formation of the adhesive substrate, formation of an organic solvent Removal and others (synthesis of a polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound, synthesis of the active hydrogen group-containing compound, etc.) are performed.

The aqueous medium phase can be prepared, for example, by dispersing the resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin microparticles | fine-particles, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.
The toner solution is prepared by mixing the active hydrogen group-containing compound, the polymer capable of reacting with the active hydrogen group-containing compound, the crystalline polyester resin, the colorant, the release agent, the charging agent in the organic solvent. It can be carried out by dissolving or dispersing a toner material such as a control agent and the unmodified polyester resin.
In the toner material, components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound are added when the resin fine particles are dispersed in the aqueous medium in the aqueous medium phase preparation. The toner solution may be added and mixed in the aqueous medium, or may be added to the aqueous medium phase together with the toner solution when the toner solution is added to the aqueous medium phase.

The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. For example, the boiling point is less than 150 ° C. in terms of ease of removal. Volatile ones are preferred, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, acetic acid Examples include ethyl, methyl ethyl ketone, and methyl isobutyl ketone. Among these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner materials, and 60-140 mass parts is preferable. More preferably, 80-120 mass parts is still more preferable.

The dispersion can be prepared by emulsifying and dispersing the previously prepared toner solution in the previously prepared aqueous medium phase. In the emulsification / dispersion, when the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a crosslinking reaction, the adhesive base material is generated.
The adhesive substrate (for example, the urea-modified polyester resin) includes, for example, (1) a polymer that can react with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)). The toner solution is emulsified and dispersed in the aqueous medium phase together with the active hydrogen group-containing compound (for example, the amines (B)) to form a dispersion, and both are subjected to an extension reaction or the like in the aqueous medium phase. (2) The toner solution is emulsified and dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance to form a dispersion, and in the aqueous medium phase (3) The toner solution may be added to and mixed with the aqueous medium, and then the active hydrogen group-containing material may be formed. The compound was added to form a dispersion, it may be generated by elongation reaction or crosslinking reaction from particle interfaces in the aqueous medium phase. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.

  The reaction conditions for producing the adhesive base material by the emulsification / dispersion are not particularly limited, depending on the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours, and the reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.

In the aqueous medium phase, as a method for stably forming the dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), for example, In an aqueous medium phase, a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), the colorant, the mold release agent, the charge control agent, the unmodified Examples thereof include a method in which the toner solution prepared by dissolving or dispersing the toner material such as polyester resin in the organic solvent is added and dispersed by shearing force.
The dispersion is not particularly limited as a method thereof, and can be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction type. Examples include a disperser, a high-pressure jet disperser, and an ultrasonic disperser. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion can be controlled to 2 to 20 μm.
When the high-speed shearing disperser is used, conditions such as the rotation speed, dispersion time, and dispersion temperature are not particularly limited and can be appropriately selected according to the purpose. For example, the rotation speed is 1 3,000 to 30,000 rpm is preferable, 5,000 to 20,000 rpm is more preferable, and the dispersion time is preferably 0.1 to 5 minutes in the case of a batch system, and the dispersion temperature is under pressure. 0-150 degreeC is preferable and 40-98 degreeC is more preferable. The dispersion temperature is generally easier when the temperature is higher.

In the emulsification / dispersion, the amount of the aqueous medium used is preferably 50 to 2,000 parts by mass, and more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the toner material.
If the amount used is less than 50 parts by mass, the toner material may be poorly dispersed, and toner particles having a predetermined particle size may not be obtained. May be.

In the preparation of the dispersion, if necessary, a dispersant is used from the viewpoint of stabilizing the dispersion (oil droplets composed of the toner solution) and sharpening the particle size distribution while obtaining a desired shape. Is preferred.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a slightly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, and the like, and those having a fluoroalkyl group are preferable. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate ester and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (manufactured by Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC- 129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (large) Nihon Ink Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Manufactured) and the like.

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M Co.); Unidyne DS-202 (manufactured by Daikin Industries Ltd.), MegaFuck F-150 F-824 (manufactured by Dainippon Ink Co., Ltd.); Xtop EF-132 (manufactured by Tochem Products); Footgent F-300 (manufactured by Neos).

Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine and the like.

Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing hydroxyl groups, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and compounds containing carboxyl groups, amides Examples thereof include homopolymers or copolymers of compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, celluloses, and the like.
Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylic acid ester, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

In preparing the dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme.

  In the preparation of the dispersion, a catalyst for the extension reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

  The organic solvent is removed from the obtained dispersion (emulsified slurry). The organic solvent is removed by (1) a method of gradually raising the temperature of the entire reaction system to completely evaporate and remove the organic solvent in the oil droplets, and (2) spraying the emulsified dispersion in a dry atmosphere. And a method of completely removing the water-insoluble organic solvent in the oil droplets to form toner fine particles and evaporating and removing the aqueous dispersant together.

  When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like in a liquid, and the classification operation may be performed after obtaining a powder after drying.

Thus, the obtained toner particles are mixed with particles of the colorant, release agent, charge control agent, etc., and further, a mechanical impact force is applied to the release agent from the surface of the toner particles. And the like can be prevented from being detached.
As a method of applying the mechanical impact force, for example, a method of applying an impact force to the mixture with a blade rotating at high speed, an appropriate collision between particles or composite particles by introducing the mixture into a high-speed air stream and accelerating the mixture is accelerated. The method of making it collide with a board etc. are mentioned. As an apparatus used for this method, for example, an ong mill (manufactured by Hosokawa Micron), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) to reduce the pulverization air pressure, and a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

  The toner has the following volume average particle diameter (Dv), volume average particle diameter (Dv) / number average particle diameter (Dn), penetration, low temperature fixability, offset-free temperature, thermal characteristics, image It is preferable to have a concentration.

The volume average particle diameter (Dv) of the toner is preferably, for example, 3 to 8 μm, and more preferably 4 to 7.
When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier may be reduced. In the developer, toner filming on the developing roller and toner fusion to a member such as a blade are likely to occur because the toner is thinned. When the thickness exceeds 8 μm, the resolution is high and high. It becomes difficult to obtain an image of an image quality, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner may increase.

The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the toner is, for example, preferably 1.20 or less, and more preferably 1.15 or less.
When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is 1.20 or less, the toner has a relatively sharp particle size distribution and is fixed to a recording medium having a rough surface. Fixing performance is improved because the amount of fine toner that is difficult to apply pressure sometimes decreases. On the other hand, if it exceeds 1.20, the number of coarse toner particles increases, it is difficult to obtain a high-resolution and high-quality image, and the toner particle diameter varies when the toner in the developer is balanced. May increase and the image density may fluctuate.

  The volume average particle diameter and the ratio (Dv / Dn) between the volume average particle diameter and the number average particle diameter are measured using, for example, a particle size measuring device “Multisizer II” manufactured by Beckman Coulter, Inc. Can do.

As said penetration, for example, the penetration measured by a penetration test (JIS K2235-1991) needs to be 15 mm or more, and 20-30 mm is more preferable.
When the penetration is less than 15 mm, the heat resistant storage stability may be deteriorated.
The penetration can be measured according to JIS K2235-1991. Specifically, a 50 ml glass container is filled with toner and left in a thermostatic bath at 50 ° C. for 20 hours. The penetration can be measured by cooling the toner to room temperature and performing a penetration test. In addition, it has shown that the said heat-resistant preservation | save property is excellent, so that the said penetration value is large.

As the low temperature fixability, from the viewpoint of achieving both a reduction in the fixing temperature and the occurrence of no offset, it is preferable that the lower limit temperature for fixing is lower, and more preferable that the temperature at which no offset is generated is higher. As a temperature range in which both can be achieved, the minimum fixing temperature is less than 140 ° C., and the non-offset temperature is 200 ° C. or more.
The fixing lower limit temperature is, for example, an image forming apparatus, a transfer sheet is set, a copy test is performed, and the remaining ratio of the image density after rubbing the obtained fixed image with a pad is 70% or more. The fixing member temperature is the lower limit fixing temperature.
The offset non-occurrence temperature is adjusted such that the toner to be evaluated is developed with a predetermined amount by using an image forming apparatus, and is adjusted so that the temperature of the fixing member is variable, so that no offset is generated. Can be determined by measuring.

The thermal characteristics are also called flow tester characteristics, and are evaluated as, for example, a softening temperature (Ts), an outflow start temperature (Tfb), a 1/2 method softening point (T1 / 2), and the like.
These thermal characteristics can be measured by an appropriately selected method. For example, the thermal characteristics can be obtained from a flow curve measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation).
There is no restriction | limiting in particular as said softening temperature (Ts), According to the objective, it can select suitably, For example, 30 degreeC or more is preferable and 50-90 degreeC is more preferable. When the softening temperature (Ts) is less than 30 ° C., the heat resistant storage stability may be deteriorated.
There is no restriction | limiting in particular as said outflow start temperature (Tfb), According to the objective, it can select suitably, For example, 60 degreeC or more is preferable and 80-120 degreeC is more preferable. When the outflow start temperature (Tfb) is less than 60 ° C., at least one of heat resistant storage stability and offset resistance may be deteriorated.
The 1/2 method softening point (T1 / 2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 ° C. or higher is preferable, and 100 to 170 ° C. is more preferable. When the 1/2 method softening point (T1 / 2) is less than 90 ° C., the offset resistance may be deteriorated.

The image density is, for example, preferably 1.40 or more, more preferably 1.45 or more, and more preferably 1.50 or more, as measured by a spectrometer (X-Light, 938 Spectrodensitometer). Is more preferable.
If the image density is less than 1.40, the image density may be low and high image quality may not be obtained.
The image density is, for example, a solid image having a developer adhesion amount of 0.4 ± 0.05 mg / cm ^{2 on} copy paper (type 6200; manufactured by Ricoh Co., Ltd.) using Pretail 550 (manufactured by Ricoh Co., Ltd.). The surface temperature of the fixing roller is formed at a fixing lower limit temperature of + 15 ° C., and the image density at any three locations in the obtained solid image is measured using a spectrometer (938 Spectrodensitometer, manufactured by X-Light). And it can measure by calculating the average value.

  The coloration of the toner is not particularly limited and may be appropriately selected according to the purpose, and may be at least one selected from black toner, cyan toner, magenta toner, and yellow toner. Can be obtained by appropriately selecting the type of the colorant, and is preferably a color toner.

In the fixing step, the fixed image formed by fixing the image with the toner on the recording medium preferably has the following smear property.
As the smearing property, for example, using a spectrometer (X-Light Corp., 938 Spectrodensitometer) of an image attached after rubbing using a smear tester (friction tester type I, JIS L0823). For example, the measured density value (smear ID) is evaluated based on the fixing temperature when it is 0.3 or less, and the lower the fixing temperature, the better.
The smear ID is such that, for example, a pre-tail 550 (manufactured by Ricoh Co., Ltd.) is used, and the amount of developer adhering to copy paper (type 6200; manufactured by Ricoh Co., Ltd.) is 0.75 ± 0.1 mg / cm ^2. A halftone image is formed on the friction piece of a smear tester (friction tester type I, JIS L0823, friction piece diameter: φ15), and a white cotton cloth (JIS L0803 cotton No. 3) of about 25 × 25 mm is placed in the fiber direction. Affix with double-sided tape so that it is horizontal with the direction of movement of the friction element, rub the halftone image in five reciprocations and continuous motions, then peel off the white cotton cloth and remove any image on the friction element trace where the image is attached. The smear ID can be measured by measuring the image density at three locations using a spectrometer (938 Spectrodensimeter, manufactured by X-Light Corporation) and calculating the average value.

Hereinafter, an example of the image fixing device of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional explanatory view showing an example of the image fixing apparatus of the present invention.
A belt-type image fixing device 110 shown in FIG. 1 includes a heating roller 121, a fixing roller 122, a pressure roller 124, and a fixing belt 123.
The fixing belt 123 is stretched by a heating roller 121 and a fixing roller 122 that are rotatably arranged inside, and is heated to a predetermined temperature by the heating roller 121. The heating roller 121 has a built-in heating source 125 and is designed such that the temperature can be adjusted by a temperature sensor 127 attached in the vicinity of the heating roller 121. The fixing roller 122 is rotatably disposed inside the fixing belt 123 and in contact with the inner surface of the fixing belt 123. The pressure roller 124 is in contact with the outer side of the fixing belt 123 and the outer surface of the fixing belt 123 so as to press the fixing roller 122 so as to be rotatable.

In the belt-type image fixing device 110 shown in FIG. 1, first, the recording medium S on which the toner image T to be fixed is formed is conveyed to the heating roller 121. The toner image T on the recording medium S is heated and melted by the heating roller 121 and the fixing belt 123 heated to a predetermined temperature by the action of the built-in heating source 125. In this state, the sheet S is inserted into a nip portion N formed between the fixing roller 122 and the pressure roller 124. The recording medium S inserted into the nip N is brought into contact with the surface of the fixing belt 123 that rotates in conjunction with the rotation of the fixing roller 122 and the pressure roller 124, and the surface pressure of the nip N is 55 N / cm. ^The toner image T is fixed on the recording medium S by being pressed when passing through the nip portion N by the pressing force of the pressure roller 124 at ² or more. At this time, in the toner, the second resin existing outside the first resin is crushed by the pressing force, exists inside the second resin, and has a glass transition temperature (° C.). The first resin that is lower than the glass transition temperature (° C.) of the second resin is eluted. As a result, the toner is fixed even under low temperature fixing conditions.
Next, the recording medium S on which the toner T is fixed passes between the fixing roller 122 and the pressure roller 124, is peeled off from the fixing belt 123, and is conveyed to a tray (not shown) through a guide G. The fixing belt 123 is cleaned by the cleaning roller 126.

FIG. 2 is a schematic sectional view showing an example of the image fixing apparatus of the present invention.
An image fixing device 210 shown in FIG. 2 includes a heating roller 220 as the fixing member and a pressure roller 230 disposed in contact with the heating roller 220.
The heating roller 220 has a hollow metal cylinder 221, the surface of which is covered with an offset prevention layer 222, and a heating lamp 223 is disposed inside. The pressure roller 230 has a metal cylinder 231, and the surface thereof is covered with an offset prevention layer 232. Note that the pressure roller 230 may have a metal cylinder 231 having a hollow shape and a heating lamp 233 disposed therein.
The heating roller 220 and the pressure roller 230 are urged by a spring (not shown) so as to be rotatable in a pressure contact state, and form a nip portion N.

In the image fixing device 210 shown in FIG. 2, first, the recording medium S on which the toner image T to be fixed is formed is conveyed to the nip portion N between the heating roller 220 and the pressure roller 230. The toner T on the recording medium S is heated and melted by the heating roller 220 heated to a predetermined temperature by the action of the built-in heating lamp 223, and at the same time when passing through the nip portion N, the toner T When the surface pressure of the nip portion N is 55 N / cm ² or more, the toner image T is fixed on the recording medium S by being pressed by the pressing force of the pressure roller 230. At this time, in the toner, the second resin existing outside the first resin is crushed by the pressing force, exists inside the second resin, and has a glass transition temperature (° C.). The first resin that is lower than the glass transition temperature (° C.) of the second resin is eluted. As a result, the toner is fixed even under low temperature fixing conditions.

FIG. 3 is a schematic sectional view showing an example of the image fixing apparatus of the present invention.
3 includes a heating roller 320 as the fixing member, a pressure roller 330 disposed in contact with the heating roller 320, and electromagnetic induction disposed in the vicinity of the heating roller. An electromagnetic induction type image fixing device including a heating unit 340.
The heating roller 320 has a heat pipe 321 in which water or a fluorine-based inert liquid as a working liquid is sealed in a copper pipe container, and the surface thereof is formed by being coated with a coating 322 made of a fluororesin.
The pressure roller 330 has a metal cylinder, and its surface is formed by being covered with an elastic layer 331.
The heating roller 320 and the pressure roller 330 are urged by a spring (not shown) so as to be rotatable in a pressed state, and form a nip portion N.
The electromagnetic induction heating means 340 is disposed in the vicinity of the heating roller 320 and on the opposite side of the nip portion N over the axial direction of the heating roller 320. The electromagnetic induction heating unit 340 includes an induction coil 341 provided on the upper surface of the non-insulating shielding layer 342 and an insulating layer 343 provided on the lower surface of the shielding layer 342.

In the image fixing device 310 shown in FIG. 3, when the induction coil 341 of the electromagnetic induction heating unit 340 is energized, an alternating magnetic field is formed around the electromagnetic induction heating unit 340, close to the induction coil 341, and the induction coil 341. Thus, the heating roller 320 in the state where the lower half is surrounded is preheated uniformly and efficiently by induction of overcurrent. The recording medium S on which the toner image T to be fixed is formed is conveyed to the nip N between the heating roller 320 and the pressure roller 330. The toner T on the recording medium S is heated and melted by the heating roller 320 heated to a predetermined temperature by the action of the electromagnetic induction heating unit 340, and at the same time, when passing through the nip portion N, the nip portion The surface pressure of N is 55 N / cm ² or more and is pressed by the pressing force of the pressure roller 330, and the toner image T is fixed on the recording medium S. At this time, in the toner, the second resin existing outside the first resin is crushed by the pressing force, exists inside the second resin, and has a glass transition temperature (° C.). The first resin that is lower than the glass transition temperature (° C.) of the second resin is eluted. As a result, the toner is fixed even under low temperature fixing conditions.

FIG. 4 is a schematic sectional view showing an example of the image fixing device of the present invention.
An image fixing device 420 shown in FIG. 4 is an image fixing device (transfer simultaneous fixing type image fixing device) that can perform simultaneous transfer fixing, and is provided in the vicinity of the intermediate transfer belt 410, and the toner image T on the intermediate transfer belt 410. A transfer fixing roller 430 as a transfer fixing member to which the toner is transferred, and a pressure roller 440 arranged in contact with the roller.
The transfer and fixing roller 430 has a metal cylinder such as aluminum, and the surface thereof is covered with a release layer, and a halogen heater 431 as a heating unit is disposed therein.
The pressure roller 440 has a cored bar 441 and the surface thereof is covered with an elastic layer.
The transfer fixing roller 430 and the pressure roller 440 are rotatably provided in a pressure contact state, and form a nip portion N.
Inside the intermediate transfer belt 410, a bias roller 411 is disposed on the upstream side of the transfer portion (a nip portion between the intermediate transfer belt 410 and the transfer fixing roller 430), and a bias roller 412 is disposed in the transfer portion. .
The bias roller 411 prevents an electric field from being generated between the bias roller 411 and the transfer fixing roller 430 in order to prevent toner dust (disturbance before transfer of the toner image T) when the bias roller 411 approaches the transfer fixing roller 430 before the transfer nip. In addition, a bias having a polarity opposite to the polarity of the toner image T is applied so that an electric field in which the toner is attracted to the intermediate transfer belt 410 is generated. Instead of this, it may be grounded.
The bias roller 412 applies a bias (main bias) having the same polarity as that of the toner image T so that an electric field in which toner is electrostatically attracted to the transfer fixing roller 430 is generated in the transfer nip, and the electrostatic repulsive force is applied to the toner. To grant.

In the image fixing device 420 shown in FIG. 4, first, the toner image T transferred from the intermediate transfer belt 410 to the transfer fixing roller 430 is predetermined by the action of the halogen heater 431 until it is fixed to the recording medium S at the nip portion N. On the transfer and fixing roller 430 heated to the temperature of 1, the film is heated and melted alone. The recording medium S is sent from the registration roller pair 450 toward the nip portion N at a timing when the leading end of the toner image T on the transfer fixing roller 430 coincides with a predetermined position in the transport direction. When the recording medium S is inserted into the nip portion N, the nip portion N is pressed by the pressing force of the pressure roller 440 with a surface pressure of 55 N / cm ² or more of the nip portion N, and is transferred onto the transfer fixing roller 430. The toner image T is fixed on the recording medium S. At this time, the second resin existing outside the first resin in the toner is crushed by the pressing force and exists inside the second resin, and the glass transition temperature (° C.) thereof is the first resin. The first resin that is lower than the glass transition temperature (° C.) of the second resin is eluted. As a result, the toner is fixed even under low temperature fixing conditions.
Since the image fixing device 420 can sufficiently obtain the process of heating only the toner image T in advance, sufficient image quality can be obtained even when the heating temperature is set low, and the recording medium S is heated only by the nip portion N. Therefore, it is not heated excessively, and the adhesion between the toner image T and the recording medium S is not increased more than necessary. For this reason, low-temperature fixing is possible, the warm-up time can be shortened, and energy saving can be realized.

FIG. 5 is a schematic sectional view showing an example of the image fixing apparatus of the present invention.
An image fixing device 510 shown in FIG. 5 includes a fixing roller 520 serving as the fixing member, a pressure roller 530 disposed in contact with the fixing roller 520, and an electromagnetic induction heating source 540 that heats the fixing roller 520 and the pressure roller. An electromagnetic induction type image fixing device.
The fixing roller 520 includes a cored bar 521, and the surface thereof is formed by covering a heat insulating elastic layer 522, a heat generating layer 523, and a release layer 524 in this order. The pressure roller 530 has a metal core 531, and the surface thereof is formed by covering a heat insulating elastic layer 532, a heat generating layer 533, and a release layer 534 in this order. Note that the release layer 524 and the release layer 534 are formed of tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA).
The fixing roller 520 and the pressure roller 530 are urged by a spring (not shown) so as to be rotatable while being in pressure contact with each other, and form a nip portion N.
The electromagnetic induction heating source 540 is disposed in the vicinity of the fixing roller 520 and the pressure roller 530, respectively, and heats the heat generation layer 523 and the heat generation layer 534 by electromagnetic induction.
In the image fixing apparatus shown in FIG. 5, the fixing roller 520 and the pressure roller 530 are preheated uniformly and efficiently by the electromagnetic induction heating source 540. In addition, since the combination of the roller and the roller, a high surface pressure of the nip portion N can be easily realized.

The image fixing method of the present invention includes the first resin and the outside of the first resin, and the glass transition temperature (° C.) is higher than the glass transition temperature (° C.) of the first resin. And a toner containing at least a second resin that is incompatible with the first resin, and an image formed by the toner is fixed to the recording medium at a surface pressure of the nip portion of 55 N / cm ² or more. Therefore, the smear property is excellent, the low-temperature fixability is good, and a high-quality image can be obtained. The image fixing device of the present invention can be suitably used for the image fixing method of the present invention.

(Image forming method and image forming apparatus)
The image forming method of the present invention further includes at least a fixing step of fixing the image on a recording medium by passing an image of toner through a nip formed by contacting at least two fixing members. Other processes appropriately selected according to the process are included. In the image forming method, the image may be fixed to the recording medium by transferring an image of the toner to a recording medium and passing the recording medium on which the image has been transferred through a nip portion.
The image forming apparatus according to the present invention is capable of forming a nip portion in contact with the toner image forming means, and allowing the toner image to pass through the nip portion to fix the image on a recording medium. It has at least a fixing member, and further has other members appropriately selected as necessary. The image forming apparatus may include a transfer unit that transfers the toner image formed by the toner image forming unit to a recording medium.
The toner is present on the outer side of the first resin and the first resin, the glass transition temperature (° C.) is higher than the glass transition temperature (° C.) of the first resin, and the toner Containing at least a second resin that is incompatible with the first resin,
The surface pressure of the nip portion is 55 / cm ² or more.
The image forming method of the present invention can be preferably carried out using the image forming apparatus of the present invention. Note that when the image forming apparatus of the present invention is implemented, the image forming method of the present invention is implemented.
In the image forming method of the present invention, details such as a fixing step for fixing the image on a recording medium, a nip portion, a fixing member, and toner are as described above.

The image forming method of the present invention further includes an electrostatic latent image forming step, a toner image forming step, a transfer step, etc., and other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step, a recycling step, Including control processes.
The image forming apparatus of the present invention further includes an electrostatic latent image carrier, an electrostatic latent image forming unit, a transfer unit, and the like, and the other units selected as necessary, for example, a neutralizing unit, It has cleaning means, recycling means, control means and the like.

  The electrostatic latent image forming step can be performed by the electrostatic latent image forming unit, the toner image forming step can be performed by the toner image forming unit, and the transfer step can be performed by the transfer unit. The other steps can be performed by the other means.

<Electrostatic latent image forming step and electrostatic latent image forming means>
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image bearing member (sometimes referred to as “photoconductive insulator” or “photosensitive member”), and among the known ones The shape is preferably a drum shape, and examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. It is done. Among these, amorphous silicon or the like is preferable in terms of long life.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to.
The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotrons and corotrons.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the latent electrostatic image bearing member charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

<Toner image forming step and toner image forming means>
The toner image forming step is a step of developing the electrostatic latent image with the toner to form a visible image (toner image).
The toner image can be formed, for example, by developing the electrostatic latent image using the toner, and can be performed by the toner image forming unit.
The toner image forming unit is not particularly limited as long as it can be developed using, for example, the toner, and can be appropriately selected from known ones. Preferable examples include those having at least a developing unit capable of applying the toner to the image in a contact or non-contact manner.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer that frictionally stirs and charges the toner and a rotatable magnet roller is preferable.

  In the developing unit, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image (toner image) is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the toner, but the developer may be a one-component developer or a two-component developer.

<Transfer process and transfer means>
The transfer step is a step of transferring the toner image to a recording medium. An intermediate transfer member is used, and after the toner image is primarily transferred onto the intermediate transfer member, the toner image is secondarily transferred onto the recording medium. A transfer mode is preferable, and a primary transfer process in which a toner image is transferred onto an intermediate transfer member to form a composite transfer image by using two or more colors, preferably full color toner as the toner, and recording the composite transfer image An embodiment including a secondary transfer step of transferring onto a medium is more preferable.
In the case where the fixing step is performed using the image fixing apparatus of the present invention of the transfer simultaneous fixing type, the composite transfer image is transferred onto the fixing member in the secondary transfer step. .
The transfer can be performed, for example, by charging the electrostatic latent image carrier (photoconductor) with the use of a transfer charger, and can be performed by the transfer unit. The transfer unit includes a primary transfer unit that transfers a toner image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer unit that transfers the composite transfer image onto a recording medium. Is preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means and the secondary transfer means) is a transfer device that peels and charges the toner image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the electrophotographic toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the electrophotographic color toner removed in the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  One mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 6 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer member 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and also for transferring (secondary transfer) a developed image (toner image) onto a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 shown in FIG. 6, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 7 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 6, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and the like around the photoconductor 10. Except that the cyan developing unit 45C is arranged directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 7, the same components as those in FIG. 6 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. A tandem image forming apparatus 100 shown in FIG. 8 is a tandem color image forming apparatus. The tandem image forming apparatus 120 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 8. An intermediate transfer body cleaning device 17 for removing residual toner on the intermediate transfer body 50 is disposed in the vicinity of the support roller 15. The intermediate transfer body 50 stretched by the support roller 14 and the support roller 15 is a tandem type in which four image forming means 18 of yellow, cyan, magenta, and black are arranged in parallel and facing each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 has the same configuration as the belt-type image fixing device shown in FIG. 1, and includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus 100, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem developing device 120. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. The photosensitive member is exposed to each color image corresponding image (L in FIG. 9), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. Developing with color toner (black toner, yellow toner, magenta toner and cyan toner) to form a toner image with each color toner, and intermediate transfer of the toner image 50 includes a transfer charger 62 for transferring the toner image on the toner image 50, a photoreceptor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta) based on the image information of each color. Image and cyan image) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feeding roller 150 is rotated to feed out the sheets (recording paper) on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.
Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). At this time, the surface pressure of the nip portion between the fixing belt 26 and the pressure roller 27 is 55 N / cm ₂ or more, and in the toner, the second resin existing outside the first resin is contained in the toner. The first resin having a glass transition temperature (° C.) that is crushed by the surface pressure and lower than the glass transition temperature (° C.) of the second resin is eluted. Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the paper discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  In the image forming method and the image forming apparatus of the present invention, the toner having excellent low-temperature fixability is used, and the image is fixed at a predetermined surface pressure. Therefore, it is excellent in smearing and high image quality even under low-temperature fixing conditions. Obtained efficiently.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

(Production Example 1)
<Adhesive substrate production process>
In the following manner, an adhesive base material as the first resin was produced in the form of particles to produce a toner.

-Preparation of toner solution-
--- Synthesis of unmodified polyester (low molecular polyester)-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 220 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 561 parts by mass of bisphenol A propion oxide 3 mol adduct, 218 parts by mass of terephthalic acid, 48 masses of adipic acid And 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, after reacting the reaction solution under a reduced pressure of 10 to 15 mmHg for 5 hours, 45 parts by mass of trimellitic anhydride was added to the reaction vessel, and the reaction was performed at 180 ° C. for 2 hours under normal pressure. A modified polyester was synthesized.
The obtained unmodified polyester had a number average molecular weight (Mn) of 2,500, a weight average molecular weight (Mw) of 6,700, a glass transition temperature (Tg) of 43 ° C., and an acid value of 25.

-Preparation of master batch (MB)-
40 parts by mass of carbon black (“Regal 400R”; manufactured by Cabot) as a colorant, polyester resin (“RS801”; manufactured by Sanyo Chemical Industries, Ltd., acid value = 10, weight average molecular weight (Mw) = 20,000, glass transition Temperature (Tg) = 64 ° C.) and 30 parts by mass of water were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was kneaded for 45 minutes at 130 ° C. with two rolls, rolled and cooled, and pulverized to a size of 1 mm in diameter with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch.

-Preparation of organic solvent phase-
In a reaction vessel in which a stir bar and a thermometer are set, 378 parts by mass of the unmodified polyester, 110 parts by mass of carnauba wax, 22 parts by mass of CCA (“salicylic acid metal complex E-84”; manufactured by Orient Chemical Industries), and the organic 947 parts by mass of ethyl acetate as a solvent was added, the temperature was raised to 80 ° C. with stirring, the temperature was maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts by mass of the master batch and 500 parts by mass of ethyl acetate were charged into a reaction vessel and mixed for 1 hour to obtain a raw material solution.
1324 parts by mass of the obtained raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.), the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / sec, and 0.5 mm zirconia. The carbon black and carnauba wax were dispersed by three passes under the condition of 80% by volume of beads. Subsequently, 1324 parts by mass of a 65% by mass ethyl acetate solution of the unmodified polyester was added to the wax dispersion. One pass was performed in a bead mill under the same conditions as described above, and the mixture was dispersed to prepare an organic solvent phase.
The solid content concentration (130 ° C., 30 minutes) of the obtained organic solvent phase was 50% by mass.

--Synthesis of prepolymer--
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, trimellitic anhydride 22 parts by mass of acid and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10-15 mHg for 5 hours, and the intermediate polyester was synthesize | combined.
The resulting intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.
Next, 410 parts by mass of the intermediate polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are charged in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Thus, a prepolymer (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized.
The free isocyanate content of the obtained prepolymer was 1.53% by mass.

--Synthesis of ketimine (the active hydrogen group-containing compound)-
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (the active hydrogen group-containing compound).
The amine value of the obtained ketimine compound (the active hydrogen machine-containing compound) was 418.

  Into a reaction vessel, 648 parts by mass of the organic solvent phase, 154 parts by mass of the prepolymer, and 6.6 parts by mass of the ketimine compound are charged, and 5,000 rpm using a TK homomixer (manufactured by Tokushu Kika). A toner solution was prepared by mixing for 1 minute.

-Preparation of dispersion-
--Preparation of fine particle dispersion--
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts by weight of water, 11 parts by weight of sodium salt of ethylene oxide methacrylate adduct sulfate ("Eleminol RS-30"; manufactured by Sanyo Chemical Industries), 83 parts by weight of styrene , 83 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate, 1 part by weight of divinylbenzene, and 1 part by weight of ammonium persulfate were stirred and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Subsequently, 30 parts by mass of a 1% by mass ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours to add vinyl resin particles (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide addition) as the second resin. An aqueous dispersion (fine particle dispersion) of a sodium sulfate copolymer) was prepared.
The volume average particle size of the fine particles contained in the obtained fine particle dispersion was measured with a particle size distribution measuring apparatus (“LA-920”; manufactured by Horiba, Ltd.) using a laser light scattering method, and found to be 105 nm. . Further, when a part of the fine particle dispersion was dried to isolate the resin, and the glass transition temperature (Tg) of the resin was measured, it was 65 ° C. and the weight average molecular weight (Mw) was measured. 000.

-Preparation of aqueous medium-
990 parts by weight of water, 83 parts by weight of the fine particle dispersion, 37 parts by weight of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”; manufactured by Sanyo Chemical Industries), and 90 parts by weight of ethyl acetate, Mixing and stirring were performed to obtain a milky white liquid (aqueous medium).

--Emulsification / Dispersion--
809 parts by mass of the toner solution was added to 1200 parts by mass of the aqueous medium, and the mixture was mixed with the TK homomixer at a rotational speed of 13,000 rpm for 20 minutes to prepare a dispersion (emulsified slurry).

Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain a dispersed slurry.
The obtained dispersion slurry had a volume average particle size of 5.7 μm and a number average particle size of 5.0 μm as measured by Multisizer II (manufactured by Beckman Coulter, Inc.).

--- Washing and drying--
After filtering 100 parts by mass of the dispersion slurry under reduced pressure, adding 300 parts by mass of ion exchange water to the filter cake, mixing with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtering three times. And a final filter cake was obtained.
Here, the obtained final filter cake was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with a mesh of 75 μm to obtain toner base particles of Production Example 1.
The obtained toner base particles were observed with a scanning electron microscope (SEM) (S-900, manufactured by Hitachi, Ltd.). The SEM photograph at this time is shown in FIG. From the SEM photograph, it was found that resin fine particles were present on the surface of the toner base particles and covered the surface of the toner base particles.

  Further, the glass transition temperature (Tg) of the adhesive base material as the first resin in the toner base particles was measured using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation) as follows. . First, about 10 mg of toner base particles were placed in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 min, and the sample was cooled to room temperature and left for 10 min. Then, the DSC curve was measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, using the analysis system in the TG-DSC system TAS-100 system, the glass transition temperature (Tg) is calculated from the contact point between the tangent line of the endothermic curve near the glass transition temperature (Tg) and the baseline. did. Here, the glass transition temperature (Tg) was measured twice, and the second run value was adopted. As a result, the glass transition temperature (Tg) of the adhesive substrate as the first resin was 51 ° C. The glass transition temperature (Tg) of the resin fine particles as the second resin is 65 ° C. as described above, and the glass transition temperature of the second resin is higher than the glass transition temperature of the first resin. Was confirmed.

--External additive treatment--
Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) was added to 100 parts by mass of the toner base particles of Production Example 1 with 1.0 part by mass of hydrophobic silica as an external additive and 0.5 parts by mass of hydrophobic titanium oxide. The toner of Production Example 1 was produced by mixing using the toner.

  With respect to the obtained toner, the volume average particle size (Dv), number average particle size (Dn), and particle size distribution (volume average particle size (Dv) / number average particle size (Dn)) were measured by the following methods.

<Toner particle size>
The volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner were measured using a particle size measuring device (“Multisizer II”; manufactured by Beckman Coulter, Inc.) at an aperture diameter of 100 μm. From these results, the particle size distribution (volume average particle diameter (Dv) / number average particle diameter (Dn)) was calculated. As a result, the volume average particle size was 5.7 μm, the number average particle size was 5.0 μm, and the particle size distribution (Dv / Dn) was 1.14. The results are shown in Table 1.

(Production Example 2)
-Preparation of toner base particles-
Toner base particles of Production Example 2 were obtained in the same manner as in Production Example 1 except that the crystalline polyester resin synthesized by the following method was added in Production Example 1.

--Synthesis of crystalline polyester resin--
Into a 5-liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, 2070 g of 1,4-butanediol, 2535 g of fumaric acid, 291 g of trimellitic anhydride, and 4.9 g of hydroquinone are placed. After reacting at 160 ° C. for 5 hours, the temperature was raised to 200 ° C. and reacted for 1 hour, and further reacted at 8.3 kPa for 1 hour to obtain a crystalline polyester resin. The endothermic peak temperature of DSC is 123 ° C. The molecular weight distribution by GPC of the soluble part of orthodichlorobenzene is 2,100 in weight average molecular weight (Mw), 710 in number average molecular weight (Mn), and 2.96 in Mw / Mn. It was.

--Preparation of crystalline polyester resin dispersion--
In a metal 2 L container, 100 g of the crystalline polyester resin and 400 g of ethyl acetate were taken and dissolved by heating at 79 ° C., and then cooled in an ice-water bath. To this, 500 ml of glass beads (3 mmφ) was added and pulverized for 10 hours with a batch type sand mill (made by Campehapio Co., Ltd.), after which part of ethyl acetate was distilled off, the volume average particle size was 0.4 μm, solid content A crystalline polyester resin dispersion having a concentration of 50% by mass was prepared.

In the preparation of the toner solution of Production Example 1, 200 parts by mass of the crystalline polyester resin dispersion was added to the wax dispersion together with 1324 parts by mass of a 65% by mass ethyl acetate solution of an unmodified polyester resin. Toner base particles of Production Example 2 were obtained in the same manner as Production Example 1, except that the parts were evaporated.
The obtained toner base particles were observed with a scanning electron microscope (SEM) (manufactured by Hitachi, Ltd., S-900). I found out.
Further, the glass transition temperature (Tg) of the adhesive base material as the first resin and the resin fine particles as the second resin in the toner base particles was measured in the same manner as in Production Example 1. Here, in the same manner as in Production Example 1, the measured value was a second run value. As a result, the glass transition temperature (Tg) of the first resin was 46 ° C. In addition, the glass transition temperature (Tg) of the resin fine particles as the second resin is 65 ° C. as described above, and the glass transition temperature of the second resin is higher than the glass transition temperature of the first resin. Was confirmed.

-External additive treatment-
External toner was added to the obtained toner base particles of Production Example 2 in the same manner as in the toner base particles of Production Example 1 to produce the toner of Production Example 2. With respect to the toner of Production Example 2, various physical properties and the like were measured in the same manner as Production Example 1. As a result, the volume average particle size (Dv) was 5.3 μm, the number average particle size (Dn) was 4.7 μm, and the particle size distribution (Dv / Dn) was 1.13.

  Next, Production Examples 1 and 2 were prepared in a conventional manner from 5% by mass of each of the toners of Production Examples 1 and 2 treated with the external additive and 95% by mass of a copper-zinc ferrite carrier having an average particle diameter of 40 μm coated with a silicone resin. Each developer was prepared.

Example 1
Using the developers obtained in Production Examples 1 and 2, a toner image is formed as follows, the toner image is fixed on a recording medium, and (a) fixability (smear property, minimum fixing temperature, and (Offset non-occurrence temperature), (b) image density, and (c) heat resistant storage stability were measured.

A toner image was formed and fixed on a recording medium using an image forming apparatus including the belt-type image fixing device 110 shown in FIG.
In the belt-type image fixing device 110 shown in FIG. 1, a belt tension of 1.5 kg / piece, a belt speed of 170 mm / sec, and a nip width of 6.8 mm are obtained by the fixing roller 122, the pressure roller 124, the heating roller 121, and the fixing belt 123. Fixing was performed under fixing conditions with a nip pressure of 60 N / cm ² .
The fixing roller 122 is a roller made of silicone foam having a diameter of 38 mm and an Asker C hardness of about 30 degrees. The pressure roller 124 is a roller having a diameter of 50 mm and an Asker C hardness of about 75 degrees, in which a 1 mm-thick silicone rubber layer is coated on a 48-mm diameter metal core (made of iron, thickness 1 mm) and a PFA tube is further coated. . The heating roller 121 is an aluminum roller having a diameter of 30 mm and a wall thickness of 2 mm. The fixing belt 123 has a belt diameter of 60 mm and a belt width of 310 mm, and has a nickel rubber substrate surface of about 40 μm thickness, a silicone rubber layer of about 150 μm thickness, and a release layer of PFA of 20 μm thickness. 121 and the fixing roller 122.

(A) Fixing property <Smear property>
A toner image was formed and fixed on a recording medium using an image forming apparatus provided with the belt-type image fixing device 110 shown in FIG. That is, an unfixed image is formed on transfer paper (“Type 6200”; manufactured by Ricoh Co., Ltd.) using a color copying machine (“Pretail 550”; manufactured by Ricoh Co., Ltd.) according to Production Example 1 and Production Example 2. The halftone image with toner was adjusted so that 0.75 ± 0.1 mg / cm ² of toner was developed for each single color. The obtained image was fixed by changing the temperature of the fixing belt (heating roller) every 5 ° C. using the belt type image fixing apparatus shown in FIG.
A smear tester (friction tester I type, JIS L0823, friction piece diameter: 15φ), and a white cotton cloth (JIS L0803 cotton No. 3) of about 25 x 25 mm in the fiber direction is parallel to the moving direction of the friction piece. Attached with double-sided tape. The fixed image was rubbed in 5 reciprocating continuous operations.
Peel off the white cotton cloth and measure the image density at any three points on the friction trace where the image is adhered using a spectrometer (“X-Rite, 938 Spectrodensitometer”). The smear property was evaluated at a fixing temperature at which the smear ID was 0.3 or less, and the lower the fixing temperature, the better the smear property.

<Temperature without offset>
The temperature at which no offset was generated was measured using an image forming apparatus provided with the belt fixing device shown in FIG. That is, an unfixed image is formed on transfer paper (“Type 6200”; manufactured by Ricoh Co., Ltd.) using a color copying machine (“Pretail 550”; manufactured by Ricoh Co., Ltd.) according to Production Example 1 and Production Example 2. The solid image of each single color of toner was adjusted so that 0.8 ± 0.05 mg / cm ² of toner was developed for each single color. The obtained unfixed image was fixed using the belt fixing device shown in FIG. 1 while changing the temperature of the fixing belt (heating roller) at intervals of 5 ° C., and the fixing temperature at which no offset occurred (offset non-occurrence temperature) was measured.

<Fixing temperature limit>
The minimum fixing temperature was measured using an image forming apparatus equipped with the belt fixing device shown in FIG. That is, an unfixed image is formed on transfer paper (“Type 6200”; manufactured by Ricoh Co., Ltd.) using a color copying machine (“Pretail 550”; manufactured by Ricoh Co., Ltd.) according to Production Example 1 and Production Example 2. Each single color solid image of toner was adjusted so that 0.8 ± 0.05 mg / cm ² of toner was developed. The obtained unfixed image was fixed using the belt fixing device of FIG. 1 while changing the temperature of the fixing belt (heating roller) every 5 ° C. The lowest fixing belt (roller) temperature at which the residual ratio of the image density after rubbing the obtained fixed image with sand eraser (LION GAZA) becomes 70% or more was defined as the minimum fixing temperature.

(B) Image Density Image density was measured using an image forming apparatus provided with the belt fixing device shown in FIG. That is, an unfixed image is formed on transfer paper (“Type 6200”; manufactured by Ricoh Co., Ltd.) using a color copying machine (“Pretail 550”; manufactured by Ricoh Co., Ltd.) according to Production Example 1 and Production Example 2. A solid image of each single color of toner was prepared such that 0.4 ± 0.05 mg / cm ² of toner was developed. The obtained unfixed image was fixed at a fixing belt (heating roller) surface temperature of the fixing lower limit temperature + 15 ° C. The image density at three arbitrary positions in the obtained fixed image was measured using a spectrometer (“938 Spectrodensitometer, manufactured by X-Rite”. The image density value is an average value of the image densities at three positions. It should be noted that the higher the obtained image density value, the higher the image density and the higher the density image can be formed.

(Examples 2 to 5)
In Example 1, except that the nip pressure of the nip portion N formed between the fixing roller 122 and the pressure roller 124 in the belt-type image fixing device 110 shown in FIG. 1 was changed to the nip pressure shown in Table 2. In the same manner as in Example 1, the fixed images of Examples 2 to 5 were formed and subjected to various evaluations. The results are shown in Table 2.

(Comparative Examples 1-2)
In Example 1, except that the nip pressure of the nip portion N formed between the fixing roller 122 and the pressure roller 124 in the belt-type image fixing device 110 shown in FIG. 1 was changed to the nip pressure shown in Table 2. The fixed images of Comparative Examples 1 and 2 were formed by the same method as in Example 1, and various evaluations were performed. The results are shown in Table 2.

  From the results in Table 2, the following is clear. That is, in Examples 1 to 5 where the nip pressure (surface pressure) of the nip portion N is high, a fixed image having excellent smearing properties was obtained. Further, it was found that the image was excellent in hot offset resistance and low-temperature fixability, the image density evaluation result was good, and a high-quality image was obtained.

  The image fixing method and the image fixing apparatus of the present invention are suitably used for high-quality image formation because an image having excellent smearing properties and good low-temperature fixing properties can be obtained. The image forming method and the image forming apparatus of the present invention using the image fixing method and the image fixing apparatus of the present invention are suitably used for high quality image formation.

10 Photoconductor (Photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Developer Roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separating roller 53 Constant current source 55 Switching claw 56 Discharging roller 57 Discharging tray 58 Corona charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Static eliminator 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming device 110 Belt type image fixing device 120 Tandem type developer 121 Heating Roller 122 Fixing roller 123 Fixing belt 124 Pressure roller 125 Heat source 126 Cleaning roller 127 Temperature sensor 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 45 Separating roller 146 Feeding path 147 Conveying roller 148 Feeding path 150 Copying device main body 200 Feeding table 210 Image fixing device 220 Heating roller 230 Pressure roller 300 Scanner 310 Electromagnetic induction heating type image fixing device 320 Heating roller 330 Pressure roller 340 Electromagnetic induction heating means 400 Automatic document feeder (ADF)
410 Intermediate transfer belt 420 Transfer simultaneous fixing type image fixing device 430 Transfer fixing roller 440 Pressure roller 510 Electromagnetic induction heating type image fixing device 520 Fixing roller 530 Pressure roller 540 Electromagnetic induction heating source N Nip portion S Recording medium T Toner image

JP 2002-296839 A JP 2003-131517 A JP 2001-92296 A

Claims (7)

  A toner obtained by granulation in an aqueous medium, the first resin being a polyester resin, and present outside the first resin, the glass transition temperature (° C.) of which is the first resin A toner comprising at least a second resin having a glass transition temperature (° C.) higher than a resin and a crystalline polyester resin.   The toner according to claim 1, wherein the glass transition temperature of the first resin is 40 to 55 ° C.   The toner according to claim 1, wherein the glass transition temperature of the second resin is 56 to 80 ° C.   The toner according to claim 1, wherein the second resin is at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin.   The crystalline polyester resin is synthesized using at least one of diol compounds having 2 to 6 carbon atoms and derivatives thereof, and at least one of maleic acid, fumaric acid, succinic acid, and derivatives thereof. 5. The toner according to any one of 4 to 4.   The toner according to claim 1, wherein the first resin contains an unmodified polyester resin and a urea-modified polyester resin. The toner according to claim 6, wherein a mass ratio (b) / (c) between the unmodified polyester resin (b) and the crystalline polyester resin (c) is 99/1 to 50/50.